Electrolyte for secondary battery, method of preparing electrolyte, and secondary battery including electrolyte

ABSTRACT

An electrolyte for a secondary battery, the electrolyte including an ionic liquid polymer including a repeating unit represented by Formula 1: 
     
       
         
         
             
             
         
       
         
         
           
             wherein, in Formula 1, CY, R 1 , R 2 , R 3 , X 1   − , n, and m are the same as described in the specification.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to and the benefit of Korean PatentApplication No. 10-2015-0101991, filed on Jul. 17, 2015, in the KoreanIntellectual Property Office, and all the benefits accruing therefromunder 35 U.S.C. § 119, the content of which is incorporated herein inits entirety by reference.

BACKGROUND

1. Field

The present disclosure relates to an electrolyte for a secondarybattery, a method of preparing the electrolyte, and a secondary batteryincluding the electrolyte.

2. Description of the Related Art

Secondary batteries, for example, lithium secondary batteries, have oneof the highest energy densities among commercialized secondarybatteries. Lithium secondary batteries are used in various fields, forexample, electrical vehicles.

When lithium metal or a lithium metal alloy is used as a negativeelectrode of a lithium secondary battery containing a liquidelectrolyte, the lithium metal or the lithium metal alloy may bedegraded due to the reactivity of lithium with moisture or oxygen. Inaddition, dendrites can be formed on the lithium metal or the lithiummetal alloy negative electrode. Thus, a lithium secondary batteryincluding the lithium negative electrode, such as the lithium metal orthe lithium metal alloy may have decreased capacity and lifespan.Therefore, there is a need to address this chemical instability problem.

SUMMARY

Provided is an electrolyte for a secondary battery, the electrolytehaving excellent mechanical properties and ion conductivity at roomtemperature.

Provided is a method of preparing the electrolyte, whereby theelectrolyte may be readily prepared at room temperature.

Provided is a secondary battery that includes the electrode, therebyhaving excellent electrochemical stability and charging and dischargingcharacteristics.

Additional aspects will be set forth in part in the description whichfollows and, in part, will be apparent from the description, or may belearned by practice of the presented exemplary embodiments.

According to an aspect of an exemplary embodiment, an electrolyte for asecondary battery includes an ionic liquid polymer including a repeatingunit represented by Formula 1:

wherein, in Formula 1,

CY is selected from a substituted or unsubstituted non-fused 6-memberedaromatic ring, a substituted or unsubstituted fused C₁₀-C₃₀ 6-memberedaromatic ring, or a combination of at least two of the foregoingaromatic rings linked through a single bond or a C₁-C₂₀ alkylene group;

R₁, R₂, and R₃ are each independently selected from a hydrogen atom, ahalogen atom, a cyano group, a hydroxy group, a substituted orunsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₁-C₂₀alkoxy group, a substituted or unsubstituted C₁-C₂₀ heteroalkyl group, asubstituted or unsubstituted C₃-C₂₀ cycloalkyl group, a substituted orunsubstituted C₃-C₂₀ cycloalkyloxy group, a substituted or unsubstitutedC₃-C₃₀ heterocycloalkyl group, a substituted or unsubstituted C₆-C₃₀aryl group, a substituted or unsubstituted C₇-C₃₀ arylalkyl group, asubstituted or unsubstituted C₆-C₃₀ aryloxy group, a substituted orunsubstituted C₃-C₃₀ heteroaryl group, a substituted or unsubstitutedC₄-C₃₀ heteroarylalkyl group, a substituted or unsubstituted C₃-C₃₀heteroaryloxy group, and a C₂-C₂₀ alkylene oxide group, and acombination thereof; n is an integer selected from 1 to 5,000, and m isan integer selected from 1 to 1,000; and

X₁ ⁻ is at least one anion selected from BF₄ ⁻, PF₆ ⁻, AsF₆ ⁻, SbF₆ ⁻,AlCl₄ ⁻, HSO₄ ⁻, CH₃SO₃ ⁻, (CF₃SO₂)₂N⁻, Cl⁻, Br⁻, I⁻, SO₄ ⁻, PF₆ ⁻, ClO₄⁻, CF₃SO₃ ⁻, CF₃CO₂ ⁻, (C₂F₅SO₂)₂N⁻, (C₂F₅SO₂)(CF₃SO₂)N⁻, (CF₃SO₂)₂N⁻,NO₃ ⁻, Al₂Cl₇ ⁻, AsF₆ ⁻, SbF₆ ⁻, CH₃COO⁻, (CF₃SO₂)₃C⁻, (CF₃)₂PF₄ ⁻,(CF₃)₃PF₃ ⁻, (CF₃)₄PF₂ ⁻, (CF₃)₅PF⁻, (CF₃)₆P⁻, SF₅CF₂SO₃ ⁻, SF₅CHFCF₂SO₃⁻, CF₃CF₂(CF₃)₂CO⁻, (CF₃SO₂)₂CH⁻, (SF₅)₃C⁻, and (O(CF₃)₂C₂(CF₃)₂O)₂PO⁻.

According to an aspect of another exemplary embodiment, provided is amethod of preparing an electrolyte for a secondary battery, the methodincluding:

providing a monomer represented by Formula 3;

in-situ polymerizing the monomer represented by Formula 3 to obtain theelectrolyte for a secondary battery:

wherein, in Formula 3,

CY1 may be selected from a substituted or unsubstituted non-fused6-membered aromatic ring, a substituted or unsubstituted fused C₁₀-C₃₀6-membered aromatic ring, or a combination of at least two of theforegoing aromatic rings linked through a single bond or a C₁-C₂₀alkylene group;

R₄ is selected from a halogen atom, a cyano group, a hydroxy group, asubstituted or unsubstituted C₁-C₂₀ alkyl group, a substituted orunsubstituted C₁-C₂₀ alkoxy group, a substituted or unsubstituted C₁-C₂₀heteroalkyl group, a substituted or unsubstituted C₃-C₂₀ cycloalkylgroup, a substituted or unsubstituted C₃-C₂₀ cycloalkyloxy group, asubstituted or unsubstituted C₃-C₃₀ heterocycloalkyl group, asubstituted or unsubstituted C₆-C₃₀ aryl group, a substituted orunsubstituted C₇-C₃₀ arylalkyl group, a substituted or unsubstitutedC₆-C₃₀ aryloxy group, a substituted or unsubstituted C₃-C₃₀ heteroarylgroup, a substituted or unsubstituted C₄-C₃₀ heteroarylalkyl group, asubstituted or unsubstituted C₃-C₃₀ heteroaryloxy group, and a C₂-C₂₀alkylene oxide group, and a combination thereof;

m₁ may be an integer selected from 1 to 1,000;

X₂ ⁻ may be at least one anion selected from BF₄ ⁻, PF₆ ⁻, AsF₆ ⁻, SbF₆⁻, AlCl₄ ⁻, HSO₄ ⁻, CH₃SO₃ ⁻, (CF₃SO₂)₂N⁻, Cl⁻, Br⁻, I⁻, SO₄ ⁻, PF₆ ⁻,ClO₄ ⁻, CF₃SO₃ ⁻, CF₃CO₂ ⁻, (C₂F₅SO₂)₂N⁻, (C₂F₅SO₂)(CF₃SO₂)N⁻,(CF₃SO₂)₂N⁻, NO₃ ⁻, Al₂Cl₇ ⁻, AsF₆ ⁻, SbF₆ ⁻, CH₃COO⁻, (CF₃SO₂)₃C⁻,(CF₃)₂PF₄ ⁻, (CF₃)₃PF₃ ⁻, (CF₃)₄PF₂ ⁻, (CF₃)₅PF⁻, (CF₃)₆P⁻, SF₅CF₂SO₃ ⁻,SF₅CHFCF₂SO₃ ⁻, CF₃CF₂(CF₃)₂CO⁻, (CF₃SO₂)₂CH⁻, (SF₅)₃C⁻, and(O(CF₃)₂C₂(CF₃)₂O)₂PO⁻.

According to another aspect of another exemplary embodiment, a secondarybattery includes:

a positive electrode;

a negative electrode; and

an electrolyte disposed between the positive electrode and the negativeelectrode.

BRIEF DESCRIPTION OF THE DRAWINGS

These and/or other aspects will become apparent and more readilyappreciated from the following description of the exemplary embodiments,taken in conjunction with the accompanying drawings in which:

FIGS. 1A and 1B are graphs of signal intensity (arbitrary units, a. u.)versus chemical shift (parts per million, ppm) showing the results of¹H-NMR analysis of an electrolyte composition of a monomer for formingan ionic liquid polymer used in Example 1;

FIGS. 1C and 1D are graphs of signal intensity (arbitrary units, a. u.)versus chemical shift (parts per million, ppm) showing an enlarged viewof portions of FIGS. 1A and 1B, respectively;

FIGS. 2A and 2B are graphs of signal intensity (arbitrary units, a. u.)versus molecular ion mass to charge ratio (m/z) (grams per mole, g/mol)showing results of matrix assisted laser desorption and ionization-timeof flight (MALDI-TOF) analysis of the electrolyte composition of themonomer for forming an ionic liquid polymer used in Example 1;

FIGS. 3A to 3D each illustrates a schematic cross-sectional view of alithium secondary battery according to an exemplary embodiment;

FIG. 4 illustrates a schematic cross-sectional view of a pouch-typedlithium secondary battery according to an embodiment;

FIGS. 5A and 5B are scanning electron microscope (SEM) images of lithiumnegative electrodes having an electrolyte (formed negative electrodeprotective film) used in Example 4 and Comparative Example 1;

FIG. 6 is a graph of current (Amperes, A) versus potential versus Li/Li⁺(Volts, V) showing results of cyclic voltammetry (CV) analysis withregard to an electrolyte of an ionic liquid polymer prepared in Example1;

FIG. 7 is a graph of impedance Z″ (ohms, Ω) versus impedance Z′ (ohms,Ω) showing results of impedance measurements on lithium secondarybatteries (coin-cell) prepared in Examples 4 to 6 and ComparativeExample 1;

FIG. 8 is a graph of discharge capacity (milli Amperes hours per gram)versus C/D rate (Coulombs, C) showing results of discharging capacityevaluation on the lithium secondary batteries (coin-cell) prepared inExamples 4 and Comparative Example 1 that went through a formationprocess; and

FIG. 9 is a graph of discharge capacity (milli Amperes hours per gram)versus number of cycles showing results of Coulomb efficiency andlifespan characteristics evaluation on the lithium secondary batteries(coin-cell) prepared in Examples 4 and Comparative Example 1 thatunderwent a formation process.

DETAILED DESCRIPTION

Reference will now be made in detail to exemplary embodiments, examplesof which are illustrated in the accompanying drawings, wherein likereference numerals refer to like elements throughout. In this regard,the present exemplary embodiments may have different forms and shouldnot be construed as being limited to the descriptions set forth herein.Rather, these embodiments are provided so that this disclosure will bethorough and complete, and will fully convey the effects and features ofthe present disclosure and ways to implement the present disclosure willfully convey the concept of the invention to those skilled in the art.Accordingly, the exemplary embodiments are merely described below, byreferring to the figures, to explain aspects. As used herein, the term“and/or” includes any and all combinations of one or more of theassociated listed items. Expressions such as “at least one of,” whenpreceding a list of elements, modify the entire list of elements and donot modify the individual elements of the list.

Exemplary embodiments are described herein with reference to crosssection illustrations that are schematic illustrations of idealizedembodiments. As such, variations from the shapes of the illustrations asa result, for example, of manufacturing techniques and/or tolerances,are to be expected. Thus, embodiments described herein should not beconstrued as limited to the particular shapes of regions as illustratedherein but are to include deviations in shapes that result, for example,from manufacturing. For example, a region illustrated or described asflat may, typically, have rough and/or nonlinear features. Moreover,sharp angles that are illustrated may be rounded. Thus, the regionsillustrated in the figures are schematic in nature and their shapes arenot intended to illustrate the precise shape of a region and are notintended to limit the scope of the present claims. In the drawings, likereference numerals denote like elements throughout, and thus redundantdescription thereof will be omitted.

It will be understood that, although the terms first, second, third etc.may be used herein to describe various elements, components, regions,layers, and/or sections, these elements, components, regions, layers,and/or sections should not be limited by these terms. These terms areonly used to distinguish one element, component, region, layer, orsection from another element, component, region, layer, or section.Thus, a first element, component, region, layer, or section discussedbelow could be termed a second element, component, region, layer, orsection without departing from the teachings of the present embodiments.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting. As used herein, thesingular forms “a,” “an,” and “the” are intended to include the pluralforms as well, unless the context clearly indicates otherwise.

The term “or” means “and/or.” As used herein, the terms such as“comprising”, “including”, “having”, or the like are intended toindicate the existence of the features regions, integers, steps,operations, components, and/or elements disclosed in the specification,and are not intended to preclude the possibility that one or more otherfeatures or elements may exist or may be added.

It will also be understood that when an element such as a layer, aregion or a component is referred to as being “on” another layer orelement, it can be directly on the other layer or element, orintervening layers, regions, or components may also be present. Incontrast, when an element is referred to as being “directly on” anotherelement, there are no intervening elements present.

In the drawings, the sizes of elements are exaggerated or reduced forease of description. The size or thickness of each element shown in thedrawings are arbitrarily illustrated for better understanding or ease ofdescription, and thus the present disclosure is not limited thereto.

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which this general inventive conceptbelongs. It will be further understood that terms, such as those definedin commonly used dictionaries, should be interpreted as having a meaningthat is consistent with their meaning in the context of the relevant artand the present disclosure, and will not be interpreted in an idealizedor overly formal sense unless expressly so defined herein.

“About” or “approximately” as used herein is inclusive of the statedvalue and means within an acceptable range of deviation for theparticular value as determined by one of ordinary skill in the art,considering the measurement in question and the error associated withmeasurement of the particular quantity (i.e., the limitations of themeasurement system). For example, “about” can mean within one or morestandard deviations, or within ±30%, 20%, 10%, 5% of the stated value.

Hereinafter, with reference to attached drawings, an electrolyte for asecondary battery, a method of preparing the electrolyte, and asecondary battery including the electrolyte according to an exemplaryembodiment will be described in detail. However, these are forillustrative purposes only and are not intended to limit the scope ofthe inventive concept. The scope of the inventive concept is indicatedby the claims rather than by the detailed description.

It will be understood that the term “a combination thereof” as usedherein refers to a mixture or combination inclusive of two or morecomponents.

According to an exemplary embodiment, an electrolyte for a secondarybattery may include an ionic liquid polymer including a repeating unitrepresented by Formula 1:

wherein, in Formula 1,

CY may be selected from a substituted or unsubstituted non-fused6-membered aromatic ring, a substituted or unsubstituted fused C₁₀-C₃₀6-membered aromatic ring, or a combination of at least two of theforegoing aromatic rings linked through a single bond or a C₁-C₂₀alkylene group;

R₁, R₂, and R₃ may be each independently selected from a hydrogen atom,a halogen atom, a cyano group, a hydroxy group, a substituted orunsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₁-C₂₀alkoxy group, a substituted or unsubstituted C₁-C₂₀ heteroalkyl group, asubstituted or unsubstituted C₃-C₂₀ cycloalkyl group, a substituted orunsubstituted C₃-C₂₀ cycloalkyloxy group, a substituted or unsubstitutedC₃-C₃₀ heterocycloalkyl group, a substituted or unsubstituted C₆-C₃₀aryl group, a substituted or unsubstituted C₇-C₃₀ arylalkyl group, asubstituted or unsubstituted C₆-C₃₀ aryloxy group, a substituted orunsubstituted C₃-C₃₀ heteroaryl group, a substituted or unsubstitutedC₄-C₃₀ heteroarylalkyl group, a substituted or unsubstituted C₃-C₃₀heteroaryloxy group, and a C₂-C₂₀ alkylene oxide group, and acombination thereof;

n may be an integer selected from 1 to 5,000, and m may be an integerselected from 1 to 1,000; and

X₁ ⁻ may be at least one anion selected from BF₄ ⁻, PF₆ ⁻, AsF₆ ⁻, SbF₆⁻, AlCl₄ ⁻, HSO₄ ⁻, CH₃SO₃ ⁻, (CF₃SO₂)₂N⁻, Cl⁻, Br⁻, I⁻, SO₄ ⁻, PF₆ ⁻,ClO₄ ⁻, CF₃SO₃ ⁻, CF₃CO₂ ⁻, (C₂F₅SO₂)₂N⁻, (C₂F₅SO₂)(CF₃SO₂)N⁻,(CF₃SO₂)₂N⁻, NO₃ ⁻, Al₂Cl₇ ⁻, AsF₆ ⁻, SbF₆ ⁻, CH₃COO⁻, (CF₃SO₂)₃C⁻,(CF₃)₂PF₄ ⁻, (CF₃)₃PF₃ ⁻, (CF₃)₄PF₂ ⁻, (CF₃)₅PF⁻, (CF₃)₆P⁻, SF₅CF₂SO₃ ⁻,SF₅CHFCF₂SO₃ ⁻, CF₃CF₂(CF₃)₂CO⁻, (CF₃SO₂)₂CH⁻, (SF₅)₃C⁻, and(O(CF₃)₂C₂(CF₃)₂O)₂PO⁻.

In search of a new negative active material for secondary batteries, toreplace conventional carbonaceous materials, such as graphite, researchon metal oxides, such as silicon or tin oxide having a high theoreticalcapacity and a lithium metal having the highest ion capacity (of about4200 mAh/g) has been actively conducted.

However, using the lithium metal or the like in secondary batteries maybe problematic due to a danger of explosion caused by the highreactivity of the lithium metal or the like with moisture or oxygen.

The main cause of this problem is the growth of dendrites on the surfaceof lithium metal or the like, which causes formation of dead lithium.The growth of dendrites occurs when a dissociated lithium salt or asolvent in an electrolyte of a secondary battery is partially decomposedthrough an electrochemical reaction, and the decomposition reactionproducts are accumulated on the lithium metal or the like. As thesecondary battery undergoes charging and discharging, the grown dendritemay be separated from the surface of the lithium metal or the like,making it difficult to contact the electrode. Thus, there is a problemof drastic decrease of capacity and cycle characteristics in suchbatteries.

The electrolyte for a secondary battery according to an exemplaryembodiment may include CY in Formula 1, and thus, the electrolyte mayhave improved mechanical properties even without including across-linking agent or inorganic particles, unlike conventional ionicliquids or ionic liquids polymer.

CY in Formula 1 may be selected from a substituted or unsubstitutednon-fused 6-membered aromatic ring, a substituted or unsubstituted fusedC₁₀-C₃₀ 6-membered aromatic ring, or a combination of at least two ofthe foregoing aromatic rings linked through a single bond or a C₁-C₂₀alkylene group. The non-fused 6-membered aromatic ring may be a benzenering. The term “fused C₁₀-C₃₀ 6-membered aromatic ring” as used hereinrefers to a polycyclic aromatic ring having a relatively large number ofcarbon atoms, for example, a number of carbon atoms in a range of about10 to about 30, and formed by linking benzene rings.

CY in Formula 1 may include 6-membered aromatic ring selected from asubstituted or unsubstituted benzene ring, a substituted orunsubstituted naphthalene ring, a substituted or unsubstitutedanthracene ring, a substituted or unsubstituted phenalene ring, asubstituted or unsubstituted phenanthrene ring, a substituted orunsubstituted pyrene ring, a substituted or unsubstituted chrysene ring,a substituted or unsubstituted naphthacene ring, a substituted orunsubstituted picene ring, a substituted or unsubstituted pentaphenering, and a substituted or unsubstituted hexacene ring, or a combinationof at least two of the foregoing linked through a single bond or aC₁-C₂₀ alkylene group. For example, CY in Formula 1 may include at leastone 6-membered aromatic ring selected from a substituted orunsubstituted benzene ring, a substituted or unsubstituted naphthalenering, and a substituted or unsubstituted anthracene ring, or acombination of at least two of the foregoing linked through a singlebond or a C₁-C₂₀ alkylene group.

Definitions of the substituents used in Formulae 1, 2, and 3 are asfollows.

An alkyl group, an alkoxy group, and an alkylene oxide group used inFormula 1 may include a “substituent” selected from a halogen atom, aC₁-C₂₀ alkyl group substituted with a halogen atom, such as CCF₃, CHCF₂,CH₂F, or CCl₃, a hydroxy group, a nitro group, a cyano group, an aminogroup, an amidino group, a hydrazine group, a hydrazone group, acarboxylic acid group or a salt thereof, a sulfonic acid group or a saltthereof, and a phosphoric acid group a salt thereof; or a “substituent”substituted with at least one selected from a C₁-C₂₀ alkyl group, aC₂-C₂₀ alkenyl group, a C₂-C₂₀ alkynyl group, a C₃-C₂₀ cycloalkyl group,a C₆-C₂₀ aryl group, a C₆-C₂₀ heteroaryl group, a C₆-C₂₀ aryl alkylgroup, and a C₆-C₂₀ heteroaryl alkyl group.

When a group containing a specified number of carbon atoms issubstituted with any of the groups listed in the preceding paragraph,the number of carbon atoms in the resulting “substituted” group isdefined as the sum of the carbon atoms contained in the original(unsubstituted) group and the carbon atoms (if any) contained in thesubstituent. For example, when the term “substituted C₁-C₂₀ alkyl”refers to a C₁-C₂₀ alkyl group substituted with C₆-C₂₀ aryl group, thetotal number of carbon atoms in the resulting aryl substituted alkylgroup is C₇-C₄₀.

The halogen atom used in Formula 1, 2, and 3 as a substituent mayinclude a fluorine, bromine, chlorine, and iodine.

The C₁-C₂₀ alkyl group used in Formula 1, 2, and 3 as a substituentrefers to a group derived from a saturated branched or non-branched(straight chain or linear) C₁-C₂₀ hydrocarbon. Detailed examples thereofmay include a methyl group, an ethyl group, a propyl group, an iso-butylgroup, a sec-butyl group, a tert-butyl group, a neo-butyl group, aniso-amyl group, and a hexyl group. At least one hydrogen in the C₁-C₂₀alkyl group may be substituted with a substituent as described above.

The C₁-C₂₀ alkoxy group used in Formula 1, 2, and 3 as a substituentrefers to an alkyl group bound to an oxygen. Detailed examples thereofmay include a methoxy group, an ethoxy group, and a propoxy group. Atleast one hydrogen in the C₁-C₂₀ alkoxy group may be substituted with asubstituent, such as the substituents described in the “substituent”.

The C₁-C₂₀ heteroalkyl group used in Formula 1, 2, and 3 as asubstituent refers to an alkyl group as defined above in which at leastone carbon atom is replaced with a heteroatom selected from nitrogen(N), oxygen (O), phosphorus (P), or sulfur (S) and having carbon asremaining atoms. Non-limiting examples of the heteroalkyl aremethylthio, dimethylamino, and the like. The C₁-C₂₀ heteroalkyl groupdoes not include the C₁-C₂₀ alkoxy group.

The C₂-C₂₀ alkylene oxide group used in Formulae 1, 2, and 3 as asubstituent refers to an alkylene group bound to an oxygen. Detailedexamples thereof may include an ethylene oxide, a propylene oxide, and abutylene oxide.

The C₂-C₂₀ alkenyl group used as a substituent herein refers to a grouphaving a number of carbon atoms in a range of 2 to 20 and derived from abranched or unbranched hydrocarbon with at least one carbon-carbondouble bond. Detailed examples thereof may include vinylene andallylene.

The C₂-C₂₀ alkynyl group used as a substituent herein refers to a grouphaving a number of carbon atoms in a range of 2 to 20 and derived from abranched or unbranched hydrocarbon with at least one carbon-carbontriple bond. Detailed examples thereof may include an ethynyl group, abutenyl group, an iso-butenyl group, and an iso-propynyl group.

The C₃-C₂₀ cycloalkyl group used in Formula 1, 2, and 3 as a substituentrefers to a saturated C₁-C₂₀ hydrocarbon ring system in which one of thehydrogen atoms is removed from one of the ring carbons. Detailedexamples thereof may include a cyclopropyl group, a cyclobutyl group, acyclopentyl group, and a cyclohexyl group.

The C₁-C₂₀ cycloalkyloxy group used in Formula 1, 2, and 3 as asubstituent refers to a cycloalkyl group bound to an oxygen. Detailedexamples thereof may include a cyclopropyloxy group, a cyclobutyloxygroup, and a cyclopentyloxy group. At least one hydrogen in the C₁-C₂₀cycloalkoxy group may be substituted with a substituent, such as thesubstituents described in the “substituent”.

The C₃-C₂₀ heterocycloalkyl group used in Formula 1, 2, and 3 as asubstituent refers to a C₃-C₂₀ cycloalkyl group in which one of the ringcarbons is replaced with a heteroatom selected from nitrogen (N), oxygen(O), phosphorus (P), or sulfur (S). Detailed example thereof may includea 2-tetrahydrofuranyl group.

The C₆-C₃₀ aryl group used in Formula 1, 2, and 3 as a substituent,which is used alone or in combination, refers to an aromatic systemcontaining at least one ring. Detailed examples thereof may include aphenyl group, a naphthyl group, and a tetrahydronaphthyl group.

The C₆-C₃₀ aryloxy group used in Formula 1, 2, and 3 as a substituent,which is used alone or in combination, refers to the C₆-C₃₀ aryl groupbound to an oxygen. Detailed examples thereof may include a phenoxygroup, a naphthoxy group, and a tetrahydronaphthoxy group.

The C₃-C₃₀ heteroaryl group used as a substituent herein refers to anorganic compound including at least one hetero atom selected from N, O,P, and S, wherein the rest of the cyclic atoms are all carbon atoms.Detailed example thereof may include a pyridyl group.

The C₃-C₃₀ heteroaryloxy group used in Formula 1, 2, and 3 as asubstituent, which is used alone or in combination, refers to the C₃-C₃₀heteroaryl group bound to an oxygen. Detailed example thereof mayinclude a 2-pyridyloxy group.

The C₇-C₃₀ arylalkyl group and the C₄-C₃₀ heteroarylalkyl group used asa substituent in Formula 1, 2, and 3 refer to an alkyl group bound to anaryl group and an alkyl group bound to a heteroaryl group, respectively.

CY in Formula 1 may be bound to an alkylene group between thepyrrolidinium cations. Variable m indicates the number of carbon atomsin the alkylene group. For example, m may be an integer selected from 1to 100, for example, an integer selected from 1 to 20.

While not wishing to be bound by theory, it is understood that when thealkylene group has a number of carbon atoms within these ranges, thealkylene group may migrate with the pyrrolidinium cation, thusfacilitating migration of alkali metal ions or alkaline earth metalions, such as lithium ions, during the charging and discharging of asecondary battery. Accordingly, conductivity of lithium ions in theelectrolyte including an ionic liquid polymer may improve. In addition,the electrolyte including an ionic liquid polymer may include thealkylene group, thereby improving modulus.

The potential window of the ionic liquid polymer including thepyrrolidinium cation in Formula 1 may be have a wide potential rangefrom about −0.4 Volts (V) to about 6.2 V. Whereas the potential windowof an ionic liquid polymer including a conventional imidazolium cationis in a range of about 0.5 V to about 3.5 V.

When an electrolyte includes the ionic liquid polymer including thepyrrolidinium cation in Formula 1 having a wide potential range, theamount of products generated by partially decomposed lithium salts orsolvents due to an electrochemical reaction dissociated in theelectrolyte is significantly less than that of the electrolyte includingan ionic liquid polymer including an imidazolium cation.

Accordingly, the electrolyte including the ionic liquid polymer ofFormula 1 including the pyrrolidinium cation may have excellentelectrochemical stability even at a high voltage, for example, 3.5 V orgreater, for example, 3.8 V or greater, than the electrolyte includingan ionic liquid polymer including an imidazolium cation. Thus, a varietyof solvents may be used in the battery. In addition, due to thischaracteristic, by using the electrolyte including the ionic liquidpolymer including the pyrrolidinium cation in Formula 1, unevendistribution of charges on a surface of a lithium metal or the like maybe prevented, allowing adjusting dendrite morphology.

The weight average molecular weight (Mw) of the ionic liquid polymer maybe in a range of about 500 Daltons to about 1,000,000 Daltons, forexample, from about 10,000 Daltons to about 100,000 Daltons. While notwishing to be bound by theory, it is understood that when the weightaverage molecular weight (Mw) of the ionic liquid polymer is within thisrange, an electrolyte having improved mechanical properties and ionconductivity at room temperature may be obtained.

The ionic liquid polymer may be, for example, an ionic liquid polymerrepresented by Formula 2:

wherein, in Formula 2,

R₁′, R₂′, and R₃′ may be each independently selected from a hydrogenatom, a halogen atom, a cyano group, a hydroxy group, a substituted orunsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₁-C₂₀alkoxy group, a substituted or unsubstituted C₁-C₂₀ heteroalkyl group, asubstituted or unsubstituted C₃-C₂₀ cycloalkyl group, a substituted orunsubstituted C₃-C₂₀ cycloalkyloxy group, a substituted or unsubstitutedC₃-C₃₀ heterocycloalkyl group, a substituted or unsubstituted C₆-C₃₀aryl group, a substituted or unsubstituted C₇-C₃₀ arylalkyl group, asubstituted or unsubstituted C₆-C₃₀ aryloxy group, a substituted orunsubstituted C₃-C₃₀ heteroaryl group, a substituted or unsubstitutedC₄-C₃₀ heteroarylalkyl group, a substituted or unsubstituted C₃-C₃₀heteroaryloxy group, and a C₂-C₂₀ alkylene oxide group, and acombination thereof;

p may be an integer selected from 1 to 500, and q may be an integerselected from 1 to 100; and

X₁ ⁻ may be at least one anion selected from BF₄ ⁻, PF₆ ⁻, AsF₆ ⁻, SbF₆⁻, AlCl₄ ⁻, HSO₄ ⁻, CH₃SO₃ ⁻, (CF₃SO₂)₂N⁻, Cl⁻, Br⁻, I⁻, SO₄ ⁻, PF₆ ⁻,ClO₄ ⁻, CF₃SO₃ ⁻, CF₃CO₂ ⁻, (C₂F₅SO₂)₂N⁻, (C₂F₅SO₂)(CF₃SO₂)N,(CF₃SO₂)₂N⁻, NO₃ ⁻, Al₂Cl₇, AsF₆ ⁻, SbF₆ ⁻, CH₃COO⁻, (CF₃SO₂)₃C⁻,(CF₃)₂PF₄ ⁻, (CF₃)₃PF₃ ⁻, (CF₃)₄PF₂ ⁻, (CF₃)₅PF⁻, (CF₃)₆P⁻, SF₅CF₂SO₃ ⁻,SF₅CHFCF₂SO₃ ⁻, CF₃CF₂(CF₃)₂CO⁻, (CF₃SO₂)₂CH⁻, (SF₅)₃C⁻, and(O(CF₃)₂C₂(CF₃)₂O)₂PO⁻.

A “substituted or unsubstituted C₁-C₂₀ alkyl group”, a “substituted orunsubstituted C₁-C₂₀ alkoxy group”, and a “C₂-C₂₀ alkylene oxide group”used in Formula 2 may be the same as defined in Formula 1.

The electrolyte may include at least one selected from an alkali metalsalt and an alkaline earth metal salt. The at least one selected from analkali metal salt and an alkaline earth metal salt may include at leastone selected from LiSCN, LiN(CN)₂, LiClO₄, LiBF₄, LiAsF₆, LiPF₆,LiCF₃SO₃, Li(CF₃SO₂)₂N, Li(CF₃SO₂)₃C, LiN(SO₂F)₂, LiN(SO₂CF₃)₂,LiN(SO₂CF₂CF₃)₂, LiSbF₆, LiPF₃(CF₂CF₃)₃, LiPF₃(CF₃)₃, LiB(C₂O₄)₂, NaSCN,NaSO₃CF₃, KTFSI, NaTFSI, Ba(TFSI)₂, Pb(TFSI)₂, and Ca(TFSI)₂. Forexample, the alkali metal salt and the alkaline earth metal salt may bea lithium salt selected from LiClO₄, LiCF₃SO₃, LiBF₄, LiN(CF₃SO₂)₂,LiN(SO₂F)₂, LiPF₆, LiAsF₆, LiSbF₆, and LiPF₃(CF₂CF₃)₃.

The electrolyte including the alkali metal salt and the alkaline earthmetal salt may have excellent lithium ion mobility and ion conductivity,and may effectively suppress growth of dendrite on the surface of anegative electrode.

The amount of the alkali metal salt and the alkaline earth metal saltmay be in a range of about 0.01 part by weight to about 100 parts byweight based on 100 parts by weight of the ionic liquid polymer, forexample, about 10 parts by weight to about 100 parts by weight based on100 parts by weight of the ionic liquid polymer, for example, about 20parts by weight to about 100 parts by weight based on 100 parts byweight of the ionic liquid polymer. When an electrolyte includes thealkali metal salt and the alkaline earth metal salt within these ranges,a secondary battery including the electrolyte may have improvedelectrochemical stability and charging and discharging characteristics.

The electrolyte may further include at least one selected from a liquidelectrolyte, a solid electrolyte, a gel electrolyte, a plurality ofinorganic particles, and a separator.

The liquid electrolyte may include at least one selected from an organicsolvent, an alkali metal salt, and an alkaline earth metal salt. Theliquid electrolyte may further include an ionic liquid, if desired.

The organic solvent may include a carbonate solvent. For examples, theorganic solvent may be at least one selected from ethylene carbonate,propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methylcarbonate, fluoroethylene carbonate, γ-butyrolactone, 1,2-dimethoxyethane, diepoxy ethane, dimethylene glycol dimethyl ether, trimethyleneglycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethyleneglycol dimethyl ether, succinonitrile, sulfolane, dimethyl sulfone,ethylmethyl sulfone, diethyl sulfone, adiponitrile,1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether, andtetraphenylethylene 2,2,2-trifluoroethanol.

Descriptions for the alkali metal salt and the alkaline earth metal saltmay be the same as defined in connection with the alkali metal salt andthe alkaline earth metal salt described above, and thus will not berepeated.

The term “ionic liquid” refers to a salt in a liquid state at roomtemperature or a room temperature molten salt having a melting point ofroom temperature or less and consisting of ions. The ionic liquid may bea compound including:

i) at least one cation selected from an ammonium cation, a pyrrolidiniumcation, a pyridinium cation, a pyrimidinium cation, an imidazoliumcation, a piperidinium cation, a pyrazolium cation, an oxazolium cation,a pyridazinium cation, a phosphonium cation, a sulfonium cation, atriazole cation, and a mixture thereof; and

ii) at least one anion selected from BF₄ ⁻, PF₆ ⁻, AsF₆ ⁻, SbF₆ ⁻, AlCl₄⁻, HSO₄ ⁻, ClO₄ ⁻, CH₃SO₃ ⁻, CF₃CO₂ ⁻, (CF₃SO₂)₂N⁻, (FSO₂)₂N⁻, Cl⁻, Br⁻,I⁻, SO₄ ⁻, CF₃SO₃ ⁻, (C₂F₅SO₂)₂N⁻, and (C₂F₅SO₂)(CF₃SO₂)N⁻.

For example, the ionic liquid may be at least one selected fromN-methyl-N-propyl pyrrolidinium bis(trifluoromethanesulfonyl)imide,N-butyl-N-methyl pyrrolidinium bis(3-trifluoromethylsulfonyl)imide,1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide, and1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide.

In some embodiments, when an electrolyte includes the ionic liquid and alithium salt, a mole ratio of the ionic liquid (IL) to lithium ions (Li)(IL/Li) may be in a range of about 0.1 to about 2.0, for example, fromabout 0.2 to about 1.8, for example, from about 0.4 to about 1.5. Whilenot wishing to be bound by theory, it is understood that an electrolytehaving such a mole ratio may have excellent lithium ion mobility and ionconductivity, thus more effectively suppressing growth of lithiumdendrite on a surface of a negative electrode.

The solid electrolyte may be an organic solid electrolyte or aninorganic solid electrolyte.

Examples of the organic solid electrolyte may include a polyethylenederivative, a polyethylene oxide derivative, a polypropylene oxidederivative, a phosphate ester polymer, a polyagitation lysine, apolyester sulfide, a polyvinyl alcohol, a polyvinylidene fluoride, and apolymer including an ionic dissociation group.

Examples of the inorganic solid electrolyte may include Li₃N, LiI,Li₅NI₂, Li₃N—LiI—LiOH, Li₂SiS₃, Li₄SiO₄, Li₄SiO₄—LiI—LiOH,Li₃PO₄—Li₂S—SiS₂, Cu₃N, LiPON, Li₂S.GeS₂.Ga₂S₃, Li₂O.11Al₂O₃,(Na,Li)_(1+x)Ti_(2−x)Al_(x)(PO₄)₃ (0.1≤x≤0.9),Li_(1+x)Hf_(2−x)Al_(x)(PO₄)₃ (0.1≤x≤0.9), Na₃Zr₂Si₂PO₁₂, Li₃Zr₂Si₂PO₁₂,Na₅ZrP₃O₁₂, Na₅TiP₃O₁₂, Na₃Fe₂P₃O₁₂, Na₄NbP₃O₁₂, a Na-Silicate,Li_(0.3)La_(0.5)TiO₃, Na₅MSi₄O₁₂ (wherein M may be a rare earth element,such as Nd, Gd, or Dy) Li₅ZrP₃O₁₂, Li₅TiP₃O₁₂, Li₃Fe₂P₃O₁₂, Li₄NbP₃O₁₂,Li_(1+x)(M,Al,Ga)_(x)(Ge_(1−y)Ti_(y))_(2−x)(PO₄)₃ (wherein 0≤x≤0.8,0≤y≤1.0, and M may be Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, or Yb),Li_(1+x+y)Q_(x)Ti_(2−x)Si_(y)P_(3−y)O₁₂ (wherein 0≤x≤0.4, 0≤y≤0.6, and Qmay be Al or Ga), Li₆BaLa₂Ta₂O₁₂, Li₇La₃Zr₂O₁₂, Li₅La₃Nb₂O₁₂,Li₅La₃M₂O₁₂ (M may be Nb or Ta), and Li_(7+x)A_(x)La_(3−x)Zr₂O₁₂(wherein 0<x≤3, and A may be Zn).

The gel electrolyte may be any suitable electrolyte in gel-typed knownin the art. The gel electrolyte may include, for example, a polymer andan ionic liquid polymer. The polymer may be, for example, a solid graft(block) copolymer electrolyte.

The inorganic particle may include at least one selected from a metalhydroxide, a metal carbonate, a metal carboxylate, a metal silicate, ametal aluminosilicate, a metal carbide, a metal nitride, a metal halide,a metal nitrate, a carbon oxide, a carbonaceous material, and anorganic-inorganic composite. Examples of the inorganic particles mayinclude SiO₂, TiO₂, ZnO, Al₂O₃, BaTiO₃, graphite oxide, graphene oxide,cage-structured silsesquioxane, Li₂CO₃, Li₃PO₄, Li₃N, Li₃S₄, Li₂O,montmorillonite, and a metal-organic framework (MOF). The averagediameter of the inorganic particles may be in 1 micrometers (μm) orless, for example 500 nanometers (nm) or less, for example, 100 nm orless. In some embodiments, the average diameter of the inorganicparticles may be in a range of about 1 nm to about 100 nm. In someembodiments, the average diameter of the inorganic particles may be in arange of about 5 nm to about 100 nm. In some embodiments, the averagediameter of the inorganic particles may be in a range of about 10 nm toabout 100 nm. In some embodiments, the average diameter of the inorganicparticles may be in a range of about 10 nm to about 70 nm. In someembodiments, the average diameter of the inorganic particles may be in arange of about 30 nm to about 70 nm. When the average diameter of theinorganic particles is within these ranges, an electrolyte havingexcellent film forming properties and mechanical properties may beprepared without decrease of ion conductivity thereof.

The inorganic particles may have various shapes. For example, theinorganic particle may have a spherical shape, an elliptical shape, acubical shape, a tetrahedral shape, a pyramidal shape, an octahedralshape, a cylindrical shape, a polygonal pillar-like shape, a conicalshape, a columnar shape, a tubular shape, a helical shape, a funnelshape, a dendritic shape, or any of various common regular and irregularshapes.

Examples of the separator may include polyethylene, polypropylene,polyvinylidene fluoride, and a multilayer film of two or more layersthereof, such as a mixture multilayer film, such as apolyethylene/polypropylene two layered separator, apolyethylene/polypropylene/polyethylene three-layered separator, and apolypropylene/polyethylene/polypropylene three-layered separator. To theseparator, an alkali metal salt and an alkaline earth metal salt, forexample, an electrolyte including a lithium salt and an organic solventmay be added.

According to another aspect, a method of preparing an electrolyte for asecondary battery may include;

providing a monomer represented by Formula 3;

in-situ polymerizing the monomer represented by Formula 3 to obtain theelectrolyte:

wherein, in Formula 3,

CY1 may be selected from a substituted or unsubstituted non-fused6-membered aromatic ring, a substituted or unsubstituted fused C₁₀-C₃₀6-membered aromatic ring, or a combination of at least two of theforegoing aromatic rings linked through a single bond or a C₁-C₂₀alkylene group;

R₄ may be selected from a halogen atom, a cyano group, a hydroxy group,a substituted or unsubstituted C₁-C₂₀ alkyl group, a substituted orunsubstituted C₁-C₂₀ alkoxy group, a substituted or unsubstituted C₁-C₂₀heteroalkyl group, a substituted or unsubstituted C₃-C₂₀ cycloalkylgroup, a substituted or unsubstituted C₃-C₂₀ cycloalkyloxy group, asubstituted or unsubstituted C₃-C₃₀ heterocycloalkyl group, asubstituted or unsubstituted C₆-C₃₀ aryl group, a substituted orunsubstituted C₇-C₃₀ arylalkyl group, a substituted or unsubstitutedC₆-C₃₀ aryloxy group, a substituted or unsubstituted C₃-C₃₀ heteroarylgroup, a substituted or unsubstituted C₄-C₃₀ heteroarylalkyl group, asubstituted or unsubstituted C₃-C₃₀ heteroaryloxy group, and a C₂-C₂₀alkylene oxide group, and a combination thereof;

m₁ may be an integer selected from 1 to 1,000; and

X₂ ⁻ may be at least one anion selected from BF₄ ⁻, PF₆ ⁻, AsF₆ ⁻, SbF₆⁻, AlCl₄ ⁻, HSO₄ ⁻, CH₃SO₃ ⁻, (CF₃SO₂)₂N⁻, Cl⁻, Br⁻, I⁻, SO₄ ⁻, PF₆ ⁻,ClO₄ ⁻, CF₃SO₃ ⁻, CF₃CO₂ ⁻, (C₂F₅SO₂)₂N⁻, (C₂F₅SO₂)(CF₃SO₂)N⁻,(CF₃SO₂)₂N⁻, NO₃ ⁻, Al₂Cl₇ ⁻, AsF₆ ⁻, SbF₆ ⁻, CH₃COO⁻, (CF₃SO₂)₃C⁻,(CF₃)₂PF₄ ⁻, (CF₃)₃PF₃ ⁻, (CF₃)₄PF₂ ⁻, (CF₃)₅PF⁻, (CF₃)₆P⁻, SF₅CF₂SO₃ ⁻,SF₅CHFCF₂SO₃ ⁻, CF₃CF₂(CF₃)₂CO⁻, (CF₃SO₂)₂CH⁻, (SF₅)₃C⁻, and(O(CF₃)₂C₂(CF₃)₂O)₂PO⁻.

The “substituted or unsubstituted non-fused 6-membered aromatic ring”,“substituted or unsubstituted fused C₁₀-C₃₀ 6-membered aromatic ring”,“substituted or unsubstituted C₁-C₂₀ alkyl group”, “substituted orunsubstituted C₁-C₂₀ alkoxy group”, and “C₂-C₂₀ alkylene oxide group”used in Formula 3 may be the same as defined in Formula 1.

The in-situ polymerizing may include thermal in-situ polymerization orultraviolet (UV) in-situ polymerization at room temperature. That is, asurface of the negative electrode may be directly coated with a solutioncontaining the monomer for forming an ionic liquid polymer representedby Formula 3 to thermally polymerize or UV polymerize at roomtemperature, thereby obtaining an electrolyte including an ionic liquidpolymer including a repeating unit represented by Formula 1. Thesolution containing the monomer for forming an ionic liquid polymer maybe an organic solvent, water, or the solution containing the monomer forforming an ionic liquid polymer dissolved in a mixture solvent of theorganic solvent and water. The organic solvent may be dichloroethane.The coating method may be doctor blade, spin coating, roll coating,casting or any suitable coating method known in the art.

The thermal polymerization may be carried out at a temperature in arange of about 40° C. to about 200° C. for about 10 minutes to about 24hours. If desired, a cross-linking agent or a polymerization initiatormay be further added thereto. The cross-linking agent may serve toimprove mechanical properties of the ionic liquid polymer. Thecross-linking agent is not particularly limited, and may be abifunctional or polyfunctional acrylate compound. In some embodiments,ethylene glycol dimethacrylate may be used. The polymerization initiatoris not particularly limited, but a peroxide polymerization initiator oran azo polymerization initiator may be used. In some embodiments,benzoyl peroxide, methyl ethyl peroxide,2,2′-azobis(2-isobutyronitrile), 2,2′-azobis isobutyronitrile, or2,2′-azobis(2,4-dimethyl valeronitrile) may be used.

The UV in-situ polymerization at room temperature may be carried out bydirectly coating a surface of a negative electrode with a solutioncontaining the monomer for forming an ionic liquid polymer representedby Formula 3 and photopolymerization initiator, and drying the coatednegative electrode at room temperature for about 10 minutes to about 24hours. The photopolymerization initiator is not particularly limited,and a known photopolymerization initiator, such as a benzoinphotopolymerization initiator, an acetophenone photopolymerizationinitiator, such as 2-hydroxy-2-methyl-1-phenyl-1-propanone, or a benzylketal photopolymerization initiator may be used. For example,2-hydroxy-2-methyl-1-phenyl-1-propanone, acetophenone, benzophenone, or4-methoxybenzophenone may be used alone or as a mixture thereof.

The electrolyte may include at least one selected from an alkali metalsalt and an alkaline earth metal salt. The at least one selected from analkali metal salt and an alkaline earth metal salt may include at leastone selected from LiSCN, LiN(CN)₂, LiClO₄, LiBF₄, LiAsF₆, LiPF₆,LiCF₃SO₃, Li(CF₃SO₂)₂N, Li(CF₃SO₂)₃C, LiN(SO₂F)₂, LiN(SO₂CF₃)₂,LiN(SO₂CF₂CF₃)₂, LiSbF₆, LiPF₃(CF₂CF₃)₃, LiPF₃(CF₃)₃, LiB(C₂O₄)₂, NaSCN,NaSO₃CF₃, KTFSI, NaTFSI, Ba(TFSI)₂, Pb(TFSI)₂, and Ca(TFSI)₂. Forexample, the alkali metal salt and the alkaline earth metal salt may bea lithium salt selected from LiClO₄, LiCF₃SO₃, LiBF₄, LiN(CF₃SO₂)₂,LiN(SO₂F)₂, LiPF₆, LiAsF₆, LiSbF₆, and LiPF₃(CF₂CF₃)₃.

The electrolyte including the alkali metal salt and the alkaline earthmetal salt may have excellent lithium ion mobility and ion conductivity,and may effectively suppress growth of dendrite on the surface of anegative electrode.

The amount of the alkali metal salt and the alkaline earth metal saltmay be in a range of about 0.01 part by weight to about 100 parts byweight based on 100 parts by weight of the monomer for forming the ionicliquid polymer, for example, about 10 parts by weight to about 100 partsby weight based on 100 parts by weight of the monomer for forming theionic liquid polymer, for example, about 20 parts by weight to about 100parts by weight based on 100 parts by weight of the monomer for formingthe ionic liquid polymer. While not wishing to be bound by theory, it isunderstood that when an electrolyte includes the alkali metal salt andthe alkaline earth metal salt within these ranges, a secondary batteryincluding the electrolyte may have improved electrochemical stabilityand charging and discharging characteristics.

A secondary battery according to another aspect of the present inventiveconcept may include:

a positive electrode;

a negative electrode; and

an electrolyte disposed between the positive electrode and the negativeelectrode. The secondary battery may be a lithium secondary battery. Thelithium secondary battery may be, for example, a lithium air battery, alithium metal battery, a lithium ion battery, a lithium sulfur battery,or a lithium polymer battery.

FIGS. 3A to 3D each illustrates a schematic cross-sectional view of alithium secondary battery according to an exemplary embodiment.

As shown in FIG. 3A, a lithium secondary battery may include a positiveelectrode 21, a negative electrode 22, and an electrolyte 23 disposedtherebetween. An intermediate layer 24 may be further included betweenthe electrolyte 23 and the positive electrode 21. The intermediate layer24 may have different composition from the electrolyte 23. Theintermediate layer 24 may further include at least one selected from aliquid electrolyte, a solid electrolyte, a gel electrolyte, and aseparator.

The positive electrode 21 may be prepared by coating a positive activematerial composition including a positive active material, a conductingagent, a binder, and a solvent, and then drying the coated electrode.

Examples of the negative electrode 22 may include a lithium metal and alithium metal alloy electrode. The negative electrode 22 may be, forexample, a lithium metal thin film. The thickness of the lithium metalthin film may be 100 μm or less. For example, the lithium secondarybattery may have stable cycle characteristics even when using a lithiummetal thin film having a thickness of about 100 μm or less. For example,in the lithium secondary battery, the thickness of the lithium metalthin film may be 80 μm or less, for example, 60 μm or less. In anembodiment, the thickness of the lithium metal thin film may be in arange of about 0.1 μm to about 60 μm.

The negative electrode may be a lithium metal electrode or a lithiummetal alloy electrode, and the electrolyte may be disposed on at leastone portion of the negative electrode as a layer, a film, or a sheet.

As the electrolyte 23 is disposed on at least one portion of thenegative electrode 22 as a layer, a film, or a sheet, the surface of thenegative electrode may be mechanically and electrochemically stable.Accordingly, growth of dendrite on a surface of the negative electrode22 may be suppressed during charging and discharging of the lithiumsecondary battery, and interfacial stability between the negativeelectrode 22 and the electrolyte 23 may improve. Therefore, the lithiumsecondary battery may have improved discharging capacity, coulombefficiency, and lifespan characteristics.

The thickness of the layer, the film, or the sheet may be in a range ofabout 0.1 μm to about 100 μm, for example, about 0.1 μm to about 10 μm.When an electrolyte has a thickness within these ranges, the electrolytemay have excellent mechanical properties and ion conductivity.Accordingly, a lithium secondary battery including the electrolyte mayhave improved electrochemical stability, such as capacity, coulombefficiency, and lifespan characteristics.

As the surface of the negative electrode 22 is fully coated with theelectrolyte 23, the electrolyte 23 may serve as a protective film thatprotects the surface of the negative electrode 22. For example, a directcontact between a surface of the negative electrode 22, which isdisposed between the electrolyte 23 and the positive electrode 21, andthe electrolyte 23, which is highly reactive towards lithium, may beprevented. Therefore, the negative electrode 22 may be protected,thereby increasing the electrochemical stability of the negativeelectrode 22.

As shown in FIG. 3B, the intermediate layer 24 may have a two-layeredstructure, in which a liquid electrolyte 24 a and a solid electrolyte 24b are sequentially stacked. In this case, the liquid electrolyte 24 amay be adjacent to the electrolyte 23. Such a lithium secondary batterymay have a stacking order of negative electrode/electrolyte/intermediatelayer (liquid electrolyte/solid electrolyte)/positive electrode.

Referring to FIG. 3C, the lithium secondary battery according to anexemplary embodiment may include a separator 24 c as an intermediatelayer. Descriptions for the separator will not be repeated here, as theseparator has already been described above.

As shown in FIG. 3D, as an intermediate layer of a lithium secondarybattery according to an embodiment, a liquid electrolyte 24 a may beused. The liquid electrolyte may have the same or different compositionwith the liquid electrolyte included in the electrolyte 23.

The secondary battery, for example, a lithium secondary battery may havean operation potential in a range of about −0.1 V to about 4.5 V. Inparticular, the secondary battery, for example, the lithium secondarybattery may be used even at a high voltage of 3.5 V or greater, forexample, a voltage in a range of about 3.8 V to about 4.5 V or greater.

Regarding the negative electrode 22, an interfacial resistance (R_(i))between a lithium metal member and the protective film in a Nyquist plotobtained from impedance measurements is about 40% or greater less thanthat of a bare lithium metal at a temperature of about 25° C. When theelectrolyte is used as a protective film for a lithium metal electrodeor a lithium metal alloy electrode, an interfacial resistance is reducedcompared to a battery having a lithium metal electrode alone.Accordingly, the battery using the electrolyte as a protective film mayhave excellent electrochemical stability.

FIG. 4 illustrates a schematic cross-sectional view of a pouch-typedlithium secondary battery 100.

Referring to FIG. 4, the pouch-typed lithium secondary battery 100 mayinclude an electrode assembly 110, a lead tap 130, and an exteriormember 120 including a portion for injecting an electrolyte. Thepouch-typed lithium secondary battery 100 according to an exemplaryembodiment is a secondary battery, which is rechargeable, for example, alithium-ion battery.

The electrode assembly 110 may be accommodated in the exterior member120. The electrode assembly 110 may include a positive electrode plate111, a negative electrode plate 112, and a separator 113 disposedbetween the positive electrode plate 111 and the negative electrodeplate 112. The electrode assembly 110 may be a stacked electrodeassembly, in which the positive electrode plate 111, the separator 113,and the negative electrode plate 112 are sequentially stacked. Toprovide the pouch-typed lithium secondary battery 100 having a highpower output and large capacity, a plurality of the positive electrodeplates 111, the separators 113, and the negative electrode plates 112may be stacked.

The positive electrode plate 111 may be formed by coating a surface of apositive electrode current collector including a material, such asaluminum, with a positive active material.

The positive active material may include at least one selected fromlithium cobalt oxide, lithium nickel cobalt manganese oxide, lithiumnickel cobalt aluminum oxide, lithium iron phosphorous oxide, andlithium manganese oxide, but embodiments are not limited thereto. Anysuitable positive active material available in the art may be used.

For example, the positive active material may be a compound representedby one of the following formulae: Li_(a)A_(1−b)B′_(b)D′₂ (wherein0.90≤a≤1.8, and 0≤b≤0.5); Li_(a)E_(1−b)B′_(b)O_(2−c)D′_(c) (wherein0.90≤a≤1.8, 0≤b≤0.5, and 5≤c≤0.05); LiE_(2−b)B′_(b)O_(4−c)D′_(c)(wherein 0≤b≤0.5, and 0≤c≤0.05); Li_(a)Ni_(1−b−c)CO_(b)B′_(c)D′_(α)(wherein 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, and 0≤α≤2);Li_(a)Ni_(1−b−c)Co_(b)B′_(c)O_(2−α)F′_(α) (wherein 0.90≤a≤1.8, 0≤b≤0.5,0≤c≤0.05, and 0≤α≤2); Li_(a)Ni_(1−b−c)Mn_(b)B′_(c)D′_(α) (wherein0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, and 0≤α≤2);Li_(a)Ni_(1−b−c)Mn_(b)B′_(c)O_(2−α)F′_(α) (wherein 0.90≤a≤1.8, 0≤b≤0.5,0≤c≤0.05, and 0≤α≤2); Li_(a)Ni_(b)E_(c)G_(d)O₂ (wherein 0.90≤a≤1.8,0≤b≤0.9, 0≤c≤0.5, and 0.001≤d≤0.1); Li_(a)Ni_(b)CO_(c)Mn_(d)G_(e)O₂(wherein 0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5, and 0.001≤e≤0.1);Li_(a)NiG_(b)O₂ (wherein 0.90≤a≤1.8, and 0.001≤b≤0.1); Li_(a)CoG_(b)O₂(wherein 0.90≤a≤1.8, and 0.001≤b≤0.1); Li_(a)MnG_(b)O₂ (wherein0.90≤a≤1.8, and 0.001≤b≤0.1); Li_(a)Mn₂GbO₄ (wherein 0.90≤a≤1.8, and0.001≤b≤0.1); QO₂; QS₂; LiQS₂; V₂O₅; LiV₂O₅; LiI′O₂; LiNiVO₄;Li_((3-f))J₂(PO₄)₃ (wherein 0≤f≤2); Li_((3-f))Fe₂ (PO₄)₃ (wherein0≤f≤2); and LiFePO₄.

In the formulae above, A is nickel (Ni), cobalt (Co), manganese (Mn), ora combination thereof; B′ is aluminum (Al), nickel (Ni), cobalt (Co),manganese (Mn), chromium (Cr), iron (Fe), magnesium (Mg), strontium(Sr), vanadium (V), a rare earth element, or a combination thereof; D′is oxygen (O), fluorine (F), sulfur (S), phosphorus (P), or acombination thereof; E is cobalt (Co), manganese (Mn), or a combinationthereof; F′ is fluorine (F), sulfur (S), phosphorus (P), or acombination thereof; G is aluminum (Al), chromium (Cr), manganese (Mn),iron (Fe), magnesium (Mg), lanthanum (La), cerium (Ce), strontium (Sr),vanadium (V), or a combination thereof; Q is titanium (Ti), molybdenum(Mo), manganese (Mn), or a combination thereof; I′ is chromium (Cr),vanadium (V), iron (Fe), scandium (Sc), yttrium (Y), or a combinationthereof; and J is vanadium (V), chromium (Cr), manganese (Mn), cobalt(Co), nickel (Ni), copper (Cu), or a combination thereof.

The positive electrode active material, a binder, and a solvent may bemixed to prepare a positive active material composition.

A conducting agent may be further added to the positive active materialcomposition.

The positive active material layer composition may be directly coated ona metallic current collector and dried to form a positive electrode.Alternatively, the positive active material layer composition may becast on a support to form a positive active material layer, which maythen be separated from the support and laminated on a metallic currentcollector to form a positive electrode.

The current collector may be a metal such as nickel, aluminum, titanium,copper, gold, silver, platinum, an aluminum alloy, or stainless steel, afilm prepared by plasma-spraying or arc-spraying a carbonaceousmaterial, activated carbon fiber, nickel, aluminum, zinc, copper, tin,lead, and any alloy thereof, or a conductive film prepared by dispersinga conductive material in a rubber or a resin such asstyrene-ethylene-butylene-styrene copolymer (SEBS). For example,aluminum, nickel, or stainless steel may be used. Particularly, aluminummay be used since it can be easily processed into a thin film and isinexpensive. A shape of the current collector is not particularlylimited. For example, the current collector may have a thin film shape,a flat plate shape, a mesh shape, a net shape, a punched shape, anembossing shape, or any combination thereof, e.g. a mesh shape flatplate or the like. For example, the current collector may have an unevensurface formed by etching.

The conducting agent, the binder, and the solvent in the positive activematerial composition may be the same as those used in the negativeactive material composition. A plasticizer may further be added to thepositive active material composition and/or the negative active materialcomposition to form pores inside the electrode plates.

The amounts of the positive active material, the conductive agent, thebinder, and the solvent used in the manufacture of the lithium batteryare those levels that are generally used in the art. At least one of theconducting agent, the binder, and the solvent may not be used dependingon the use and the structure of the lithium secondary battery.

The negative electrode plate 112 may be formed by coating a surface of anegative electrode current collector including a material, such asnickel, with a negative active material. For a negative active material,a metal or metalloid alloyable with lithium, an alloy thereof, or anoxide thereof. For example, the metal or metalloid alloyable withlithium may be Si, Sn, Al, Ge, Pb, Bi, SbSi—Y′ alloy (wherein Y′ may bean alkali metal, an alkaline earth metal, Group 13 elements, Group 14elements, a transition metal, a rare earth element or a combinationthereof, except for Si), Sn—Y′ alloy (wherein Y′ may be an alkali metal,an alkaline earth metal, Group 13 elements, Group 14 elements, atransition metal, a rare earth element or a combination thereof, exceptfor Sn), or MnO_(x) (wherein 0<x≤2). Y′ may be Mg, Ca, Sr, Ba, Ra, Sc,Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru,Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ge, P,As, Sb, Bi, S, Se, Te, Po, or a combination thereof. For example, anoxide of the metal or metalloid alloyable with lithium may be a lithiumtitanium oxide, a vanadium oxide, a lithium vanadium oxide, SnO₂, orSiO_(x)(0<x<2).

In some embodiments, for the negative electrode, a lithium metal thinfilm or a metal thin film containing lithium may be used.

The amounts of the negative active material, the conductive agent, thebinder, and the solvent used in the manufacture of the lithium secondarybattery are the levels that are generally used in the art.

For an electrolyte, the electrolyte according to an exemplary embodimentmay be used. The electrolyte may be disposed between the positiveelectrode plate 111 and the negative electrode plate 112. Theelectrolyte may be on the negative electrode plate 112 as an electrolyteprotective film.

The separator 113 that is generally used in a lithium secondary batterymay be included other than the electrolyte.

The separator 113 may be an insulating thin film having a high ionpermeability and mechanical strength. The diameter of the separator 113may be in a range of about 0.01 μm to about 10 μm, and the thickness ofthe separator 113 may be in a range of about 5 μm to about 20 μm.Examples of the separator 113 may include an olefin polymer, such aspolypropylene and a sheet or a non-woven fabric including glass fiber orpolyethylene. As an electrolyte, when a solid polymer electrolyte, suchas a solid polymer, is used, the solid electrolyte may also serve as aseparator.

Detailed examples of the separator 113 may include polyethylene,polypropylene, polyvinylidene fluoride, and a multilayer film of two ormore layers thereof, such as a mixture multilayer film, such as apolyethylene/polypropylene two layered separator, apolyethylene/polypropylene/polyethylene three-layered separator, and apolypropylene/polyethylene/polypropylene three-layered separator.

The secondary battery according to an exemplary embodiment may haveexcellent capacity and lifespan characteristics. Thus, the secondarybattery 10′ may be used not only in a battery cell utilized as a powerin small-sized devices, but also in a battery pack including a pluralityof battery cells or a unit battery of a battery module as a power inmedium- or large-sized devices.

Examples of the medium- or large-sized devices may include electriccars, such as electric vehicles (EV), hybrid electric vehicles (HEV),plug-in hybrid electric vehicles (PHEV), electric two-wheeled vehicles,such as E-bikes and E-scooters, power tools, and power storage systems.However, embodiments are not limited thereto.

In addition, an electrode tab 115 may be connected to each of thepositive electrode plate 111 and the negative electrode plate 112.Electrode tabs 115 drawn from the positive electrode plate 111 and thenegative electrode plate 112, which are stacked on each other, overlapeach other, and the dense electrode tabs 115 are electrically connectedto a lead tap 130. For example, the electrode tab 115 and the lead tap130 may be connected using ultrasonic welding, etc.

The lead tap 130 may extend outside from the top of the exterior member120 and be surrounded by a tab tape 140 to increase the sealingperformance of the lead tap 130 with respect to the exterior member 120and to electrically insulate the lead tap 130 from the exterior member120.

In the pouch-typed lithium secondary battery according to an exemplaryembodiment, it is described that the electrode assembly 110 isstacked-typed, but embodiments are not limited thereto. For example, theelectrode assembly 110 may be a jelly-roll type electrode assemblymanufactured by stacking a positive electrode plate, a separator, and anegative electrode plate and winding the stacked structure.

The exterior member 120 may have a pouch-type and include an internalspace for accommodating the electrode assembly 110 and an electrolytesolution. For example, the outer surface exposed to the outside and theinner surface accommodating the electrode assembly 110 of the exteriormember 120 may include a thin metal film serving as an insulating layer.For example, the exterior member 120 may include a material, such asaluminum or stainless steel.

The exterior member 120 may include a portion for injecting anelectrolyte protruding from a side of the exterior member 120.

Hereinafter, Examples and Comparative Examples will be described indetail. However, the present examples are for illustrative purpose only,and are not intended to limit the scope of the inventive concept.

EXAMPLE Example 1 Preparation of Electrolyte

After removing impurities such as oxygen and moisture from a reactor, 10grams (g) of Starting Material (1) of Reaction Scheme 1(1-chloromethyl-4-vinylbenzene, available from Oakwood Chemical Co.,Ltd.), was added to the reactor. 6.13 g of n-methylpyrrolidine (97%,available from Sigma-Aldrich Co., Ltd) dissolved in 100 milliliters (ml)of dichloroethane was subsequently added thereto and the mixture wasstirred at a temperature of about 70° C. for about 9 hours to obtain anIntermediate Product (2) of Reaction Scheme 1. An aqueous lithiumbis(trifluoromethylsulfonyl)imide (LiTFSI, available from PANAX Co.,Ltd) solution was added to the Intermediate Product (2) at a mole ratioof about 1:1.2, and the resulting mixture was stirred at roomtemperature for about 6 hours to obtain a Monomer for Forming an IonicLiquid Polymer (3) composition of Reaction Scheme 1, in which Cl⁻ anionwas substituted with TFSI⁻ anion. To the electrolyte composition ofMonomer for Forming an Ionic Liquid Polymer (3) about 3 mole percent(mol %) of 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP) was added,based on the amount of the Monomer for Forming an Ionic Liquid Polymer(3), and the resulting mixture was coated on a Teflon support substrateby using a doctor blade. UV in-situ polymerization was performed thereonat a temperature of about 25° C. for about 30 minutes to obtain a layertyped electrolyte (thickness: about 5 micrometers (μm)) of an IonicLiquid Polymer (4) (wherein n=250), which was the final product ofReaction Scheme 1.

Example 2 Preparation of Electrolyte

A layer typed electrolyte (thickness: about 5 μm) was prepared in thesame manner as in Example 1, except that lithiumbis(trifluoromethylsulfonyl)imide (LiTFSI, available from PANAX Co.,Ltd) was further added to the electrolyte composition of Monomer forForming an Ionic Liquid Polymer (3), and the resulting mixture wasstirred to obtain an electrolyte composition. The amount of the furtheradded LiTFSI was about 25 parts by weight based on 100 parts by weightof the Monomer for Forming an Ionic Liquid Polymer (3).

Example 3 Preparation of Electrolyte

A layer typed electrolyte (thickness: about 5 μm) was prepared in thesame manner as in Example 1, except that LiTFSI was further added to theelectrolyte composition of Monomer for Forming an Ionic Liquid Polymer(3), and the resulting mixture was stirred to obtain an electrolytecomposition. The amount of the further added LiTFSI was about 100 partsby weight based on 100 parts by weight of the Monomer for Forming aIonic Liquid Polymer (3).

Example 4 Preparation of Lithium Secondary Battery (Coin-Cell)

The electrolyte composition prepared in Example 1 was coated on alithium metal member (thickness: about 25 μm) by using a doctor blade.UV in-situ polymerization was performed thereon at a temperature ofabout 25° C. for about 30 minutes to thereby prepare a lithium negativeelectrode (thickness: about 35 μm) having an electrolyte (formednegative electrode protective film) having a thickness of about 5 μm.

In a separate vessel, LiCoO₂, a conducting agent (Super-P; availablefrom Timcal, Ltd.), polyvinylidene fluoride (PVdF), and N-pyrrolidonewere mixed together to obtain a positive electrode composition. In thepositive electrode composition, a mixture weight ratio of LiCoO₂ to theconducting agent, and PVDF was about 97:1.5:1.5.

The positive electrode composition was coated on an aluminum foil(thickness: about 15 μm) and dried, first—at 25° C., and then—at about110° C. in a vacuum atmosphere, thereby preparing a positive electrode.

An electrolyte was disposed between the positive electrode obtainedaccording to the above procedure and lithium metal negative electrode tothereby prepare a lithium secondary battery (coin-cell). Apolyethylene/polypropylene separator was disposed between the positiveelectrode and the electrolyte, and a liquid electrolyte was addedthereto. The liquid electrolyte was obtained by adding a lithium saltdissolving 1.0 molar (M) LiTFSI to a mixture solvent of dimethoxy ethaneand 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether at a volumeratio of about 2:8.

Example 5 Preparation of Lithium Secondary Battery (Coin-Cell)

A lithium secondary battery (coin-cell) was prepared in the same manneras in Example 4, except that the electrolyte composition prepared inExample 2 was used instead of the electrolyte composition prepared inExample 1.

Example 6 Preparation of Lithium Secondary Battery (Coin-Cell)

A lithium secondary battery (coin-cell) was prepared in the same manneras in Example 4, except that the electrolyte composition prepared inExample 3 was used instead of the electrolyte composition prepared inExample 1.

Comparative Example 1 Preparation of Lithium Secondary Battery(Coin-Cell)

A lithium secondary battery (coin-cell) was prepared in the same manneras in Example 5, except that for a negative electrode, a lithium metalmember (thickness: about 20 μm) on a copper current collector(thickness: about 10 μm) was used.

Analysis Example 1 ¹H-NMR Analysis and MALDI-TOF Analysis 1-1. ¹H-NMRAnalysis

In order to analyze the electrolyte composition of Monomer for Formingan Ionic Liquid Polymer (3) used in Example 1, the following synthesismethod was used to perform ¹H-NMR analysis thereon.

The synthesis method of the electrolyte composition of a Monomer forForming an Ionic Liquid Polymer (3) is as follows.

First, 4-vinylbenzene, n-methylpyrrolidine, and methyl chloride weresubjected to N-methyl alkylation to obtain the Intermediate product (2)of Reaction Scheme 1. Then, an aqueous LiTFSI (available from PANAX Co.,Ltd) solution was added at a predetermined molar ratio to substitute Cl⁻anions with TFSI⁻ anions, thereby synthesizing the electrolytecomposition of Monomer for Forming an Ionic Liquid Polymer (3).

NMR 600 MHz (Model No: AVANCE III, available from Bruker Co., Ltd) wasused to perform ¹H-NMR analysis. The result of the ¹H-NMR analysis isshown in FIGS. 1A to 1D, in which FIG. 1C is an enlarged view of aportion of FIG. 1A, and FIG. 1D is an enlarged view of a portion of 1B.

Referring to FIGS. 1A and 1B, distinguishing peaks of the electrolytecomposition of a Monomer for Forming an Ionic Liquid Polymer (3) ofReaction Scheme 1 were found. That is, a C═C bond derived from a vinylgroup, a H—C═C bond derived from a benzene ring, a CH₃ group derivedfrom a methyl group, and a CH₂ bond derived from a pyrrolidinium cationwere identified. Thus, the presence of the synthesized electrolytecomposition of the Monomer for Forming an Ionic Liquid Polymer (3) ofReaction Scheme 1 was verified.

1-2. MALDI-TOF Analysis

In order to analyze the electrolyte composition of Monomer for Formingan Ionic Liquid Polymer (3) used in Example 1, the synthesis method usedin the previous section (1.1 ¹H-NMR analysis) was used to perform matrixassisted laser desorption and ionization-time of flight (MALDI-TOF)analysis.

Ultraflex III TOF/TOF 200 (available from Bruker Co., Ltd) was used inMALDI-TOF analysis. The results of MALDI-TOF analysis are shown in FIGS.2A and 2B.

Referring to FIGS. 2A and 2B, in the electrolyte composition of Monomerfor Forming an Ionic Liquid Polymer (3) of Reaction Scheme 1, thepresence of 1-methyl-1-vinylbenzyl-pyrrolidinium cation andbis(trifluoromethylsulfonyl)amide anion was found by molecular weightanalysis.

Analysis Example 2 Scanning Electron Microscope (SEM) Image

The surface of a lithium negative electrode having an electrolyte(formed the negative electrode protective film) used in Example 4 andComparative Example 1 was observed by using SEM. In SEM analysis, S-5500(available from Hitachi Co., Ltd, resolution 0.4 nanometers (nm), drivenat a voltage of about 30 kilo Volts (kV)) was used. The results thereofare shown in FIGS. 5A and 5B.

Referring to FIGS. 5A and 5B, it was found that growth of dendrite onthe surface of the lithium negative electrode having an electrolyte(formed negative electrode protective film) used in Example 4 as shownin FIG. 5A was significantly reduced compared to the growth of dendriteon the surface of the lithium negative electrode having an electrolyte(formed negative electrode protective film) used in Comparative Example1 as shown in FIG. 5B.

In addition, in order to measure a deposition density of lithium ionsdeposited on the surface of the lithium negative electrodes having anelectrolyte (formed negative electrode protective film) used in Example4 and Comparative Example 1, a method using the mass of the depositedlithium ions measured through the amount of electrons used in anelectrochemical reaction and the volume of the deposited lithium ionsmeasured through the thickness thereof was used. The results thereof areshown in Table 1.

TABLE 1 Classification Lithium deposition density (g/cm³) Example 4 0.19Comparative 0.13 Example 1

Referring to Table 1, it was found that the deposition density of thelithium ions deposited on the surface of the lithium negative electrodehaving an electrolyte (formed negative electrode protective film) usedin Example 4 was about 48% higher than the deposition density of thelithium ions deposited on the surface of the lithium negative electrodehaving an electrolyte (formed negative electrode protective film) usedin Comparative Example 1. This is because the lithium negative electrodeof Example 4 had the electrolyte (formed negative electrode protectivefilm) on the top surface thereof.

Evaluation Example 1 Cyclic Voltammetry (CV) Evaluation

CV analysis was performed on the electrolyte of the Ionic Liquid Polymer(4) (n=250) prepared in Example 1. The results thereof are shown in FIG.6.

For a CV analyzer, a potentiometer (electrochemical interface (1287ECI), available from Solartron analytical Co., Ltd.) was used.

For CV analysis, the electrolyte of the Ionic Liquid Polymer (4) (n=250)was prepared following Example 1 in a Teflon plate. Then, afree-standing polymer thin film (thickness: about 100 μm) was obtained,and was subsequently cut into a circular thin film of size of 19 cp. Acoin-cell was prepared by disposing the circular thin film between astainless-steel electrode, which is a working electrode and a lithiummetal foil, which is a reference electrode. Current value changes of thecoin-cell according to changes of potentials were measured, within avoltage range of about −0.5 V to about 6.5 V, at a scan rate of about 5milli Volts per second (mV/sec), for three cycles.

Referring to FIG. 6, a stable and reversible oxidation/reduction peakwithout a particularly low or high peak was observed within a voltagerange of about 0 Volts (V) to about 4.7 V (vs. Li/Li⁺) during threecycles. Accordingly, it was found that the electrolyte of the IonicLiquid Polymer (4) (n=250) prepared in Example 1 had excellentelectrochemical stability, even at a high voltage of 3.5 V or higher,for example, in a range of about 3.8 V to about 4.7 V (vs. Li/Li⁺).

Evaluation Example 2 Impedance Measurement-Interfacial Resistance andIon Conductivity Evaluation

With regard to lithium secondary batteries (coin-cell) prepared in thesame manner as in Examples 4 to 6 and Comparative Example 1, except thata lithium cobalt oxide electrode was used as working electrode,impedance changes according to changes of frequency of alternatingcurrent voltage were measured by using an impedance analyzer (Solartron1260A Impedance/Gain-Phase Analyzer) at a temperature of about 25° C.The amplitude was about ±10 milli Volts (mV), and the frequency rangewas in a range of about 0.1 Hertz (Hz) to about 1 mega Hertz (MHz).

Impedance measurement results 24 hours after the preparation of thelithium secondary batteries (coin-cell) prepared in Examples 4 to 6 andComparative Example 1 are shown in FIG. 7 as a Nyquist plot.

Referring to FIG. 7, the interfacial resistance of the electrode may bedetermined by the position and size of the semicircle. The differencebetween the left x side section and the right x side section of thesemicircle indicates the interface resistance at the electrode. It wasfound that the interfacial resistances of the lithium secondarybatteries (coin-cell) prepared in Examples 4 to 6 were about 42% lowerthan that of the lithium secondary battery (coin-cell) prepared inComparative Example 1.

Further, resistance values of the electrode were obtained from thecircular arc in the Nyquist plot according to the impedance measurementresults, and ion conductivities were calculated following MathematicalEquation 1. The results thereof are shown in Table 2.σ=I/R·A (σ: ion conductivity, R: resistance, I: thickness of electrolyte(protective film), A: electrode area)  Mathematical Equation 1

TABLE 2 Classification Ion conductivity (S/cm) Example 4 3.45 × 10⁻⁶Example 5 5.03 × 10⁻⁶ Example 6 6.26 × 10⁻⁶ Comparative 2.91 × 10⁻⁶Example 1

Referring to Table 2, it was found that ion conductivities of theelectrolytes in the lithium secondary batteries (coin-cell) prepared inExamples 4 to 6 was high compared to the electrolyte in the lithiumsecondary battery (coin-cell) prepared in Comparative Example 1 at atemperature of about 25° C.

Evaluation Example 3 Charging and DischargingCharacteristics-Discharging Capacity, Coulomb Efficiency, and LifespanCharacteristics 3-1. Discharging Capacity Evaluation

The lithium secondary batteries (coin-cell) prepared in Example 4 andComparative Example 1 was charged with a constant current of 0.1 Coulomb(C) rate at a temperature of about 25° C. until the voltage of the cellreached about 4.40 V (vs. Li), followed by a cut-off at a current ofabout 0.05 C rate, while maintaining a voltage of about 4.40 V in aconstant voltage mode. Afterward, the cell was discharged with aconstant current of 0.1 C rate until the voltage reached 2.8 V (vs. Li)(Formation process, 1st cycle). Formation process was completed byrepeating the charging and discharging two more times.

The lithium secondary batteries (coin-cell) that went through theformation process were charged with a constant current of 0.7 C rate ata temperature of about 25° C. at a voltage range of about 3.0 V to about4.4 V (vs. Li), followed by discharging with a constant current of about0.1 C/0.2 C/0.5 C/1.0 C/1.5 C/2.0 C until the voltage reached a cut-offvalue of 4.4 V. The results thereof are shown in FIG. 8 and Table 3.

TABLE 3 Classification @ 2.0 C 1^(st) discharging capacity (mAh/g)Example 4 125 Comparative 112 Example 1

Referring to FIG. 8 and Table 3, it was found that the 1^(st)discharging capacity at 2.0 C of the lithium secondary battery(coin-cell) prepared in Example 4 improved compared to that of thelithium secondary battery (coin-cell) prepared in Comparative Example 1.In particular, the 1^(st) discharging capacity at 2.0 C of the lithiumsecondary battery (coin-cell) prepared in Example 4 had an improvementof about 13 milli Ampere hours per gram (mAh/g) compared to that of thelithium secondary battery (coin-cell) prepared in Comparative Example 1.

Such an improvement of the 1^(st) discharging capacity may be due to theimprovement of ion conductivity of the lithium secondary battery(coin-cell) prepared in Example 4.

3-2. Coulomb Efficiency and Lifespan Characteristics Evaluation

The lithium secondary batteries (coin-cell) prepared in Example 4 andComparative Example 1 that went through the formation process, describedin section 3-1 above, was charged with a constant current of 0.7 C at atemperature of about 25° C. at a voltage range of about 3.0 V to about4.4 V (vs. Li). The lithium secondary batteries (coin-cell) weresubsequently discharged with a constant current of about 30 milliAmperes (mA) until the voltage reached a cut-off voltage of about 4.4 Vwith a constant current of 0.5 C. The same charging and dischargingprocess was repeated 99 μmes to perform total 100 μmes of charging anddischarging cycles. The results thereof are shown in FIG. 9. A Coulombefficiency and a cycle capacity retention rate were calculated byfollowing the Mathematical Equation 2 and Mathematical Equation 3,respectively. The results thereof are shown in Table 4.Coulomb efficiency (%)=[(100^(th) cycle discharging capacity/100^(th)cycle charging capacity)×100]  Mathematical Equation 2Cycle capacity retention rate (%)=[(100^(th) cycle dischargingcapacity//1^(st) cycle discharging capacity)×100]  Mathematical Equation3

TABLE 4 100^(th) Coulomb 100^(th) Cycle capacity Classificationefficiency (%) retention rate (%) Example 4 98.6 62 Comparative 98.0 43Example 1

Referring to FIG. 9 and Table 4, it was found that the 100^(th) Coulombefficiency of the lithium secondary battery (coin-cell) prepared inExample 4 was about 4% higher than that of the lithium secondary battery(coin-cell) prepared in Comparative Example 1.

In addition, it was found that the 100^(th) Cycle capacity retentionrate of the lithium secondary battery (coin-cell) prepared in Example 4was about 57% higher than that of the lithium secondary battery(coin-cell) prepared in Comparative Example 1.

As described above, according to an exemplary embodiment, theelectrolyte for a secondary battery may include the ionic liquid polymerincluding the repeating unit represented by Formula 1, improving themechanical properties and ion conductivity at room temperature. Inaddition, the method of preparing the electrolyte may be readily carriedout at room temperature. Furthermore, a secondary battery including theelectrolyte may have improved electrochemical stability and charging anddischarging characteristics.

It should be understood that exemplary embodiments described hereinshould be considered in a descriptive sense only and not for purposes oflimitation. Descriptions of features or aspects within each exemplaryembodiment should typically be considered as available for other similarfeatures or aspects in other exemplary embodiments of the presentinventive concept.

While one or more exemplary embodiments have been described withreference to the figures, it will be understood by those of ordinaryskill in the art that various changes in form and details may be madetherein without departing from the spirit and scope of the presentinventive concept as defined by the following claims.

What is claimed is:
 1. A secondary battery, comprising: a positiveelectrode; a negative electrode comprising a lithium metal or a lithiummetal alloy; and an electrolyte, wherein the electrolyte is disposedbetween the positive electrode and the negative electrode, and whereinthe electrolyte is disposed on at least one portion of the negativeelectrode as a layer, a film, or a sheet, wherein the electrolytecomprise an ionic polymer comprising a repeating unit represented byFormula 1:

wherein, in Formula 1, CY is selected from a substituted orunsubstituted non-fused 6-membered aromatic ring, a substituted orunsubstituted fused C₁₀-C₃₀ 6-membered aromatic ring, and a combinationof at least two of the foregoing aromatic rings, wherein the at leasttwo of the foregoing aromatic rings are linked through a single bond ora C₁-C₂₀ alkylene group; R₁, R₂, and R₃ are each independently selectedfrom a hydrogen atom, a halogen atom, a cyano group, a hydroxy group, asubstituted or unsubstituted C₁-C₂₀ alkyl group, a substituted orunsubstituted C₁-C₂₀ alkoxy group, a substituted or unsubstituted C₁-C₂₀heteroalkyl group, a substituted or unsubstituted C₃-C₂₀ cycloalkylgroup, a substituted or unsubstituted C₃-C₂₀ cycloalkyloxy group, asubstituted or unsubstituted C₃-C₃₀ heterocycloalkyl group, asubstituted or unsubstituted C₆-C₃₀ aryl group, an unsubstituted C₇-C₃₀arylalkyl group, a substituted or unsubstituted C₆-C₃₀ aryloxy group, asubstituted or unsubstituted C₃-C₃₀ heteroaryl group, a substituted orunsubstituted C₄-C₃₀ heteroarylalkyl group, a substituted orunsubstituted C₃-C₃₀ heteroaryloxy group, and a C₂-C₂₀ alkylene oxidegroup, and a combination thereof, provided that R₃ is not an arylalkylgroup substituted with a C₂ alkene; n is an integer up to 5,000, and mis an integer selected from 1 to 1,000, wherein the ionic polymer has aweight average molecular weight from about 500 Daltons to about1,000,000 Daltons; and X₁ ⁻ is at least one anion selected from BF₄ ⁻,PF₆ ⁻, AsF₆ ⁻, SbF₆ ⁻, AlCl₄ ⁻, HSO₄ ⁻, CH₃SO₃ ⁻, (CF₃SO₂)₂N⁻, Cl⁻, Br⁻,I⁻, SO₄ ⁻, PF₆ ⁻, ClO₄ ⁻, CF₃SO₃ ⁻, CF₃CO₂ ⁻, (C₂F₅SO₂)₂N⁻,(C₂F₅SO₂)(CF₃SO₂)N⁻, (CF₃SO₂)₂N⁻, NO₃ ⁻, Al₂Cl₇ ⁻, AsF₆ ⁻, SbF₆ ⁻,CH₃COO⁻, (CF₃SO₂)₃C⁻, (CF₃)₂PF₄ ⁻, (CF₃)₃PF₃ ⁻, (CF₃)₄PF₂ ⁻, (CF₃)₅PF⁻,(CF₃)₆P⁻, SF₅CF₂SO₃ ⁻, SF₅CHFCF₂SO₃ ⁻, CF₃CF₂(CF₃)₂CO⁻, (CF₃SO₂)₂CH⁻,(SF₅)₃C⁻, and (O(CF₃)₂C₂(CF₃)₂O)₂PO⁻.
 2. The secondary battery of claim1, wherein CY comprises 6-membered aromatic ring selected from asubstituted or unsubstituted benzene ring, a substituted orunsubstituted naphthalene ring, a substituted or unsubstitutedanthracene ring, a substituted or unsubstituted phenalene ring, asubstituted or unsubstituted phenanthrene ring, a substituted orunsubstituted pyrene ring, a substituted or unsubstituted chrysene ring,a substituted or unsubstituted naphthacene ring, a substituted orunsubstituted picene ring, a substituted or unsubstituted pentaphenering, and a substituted or unsubstituted hexacene ring, or a combinationof at least two of the foregoing linked through a single bond or aC₁-C₂₀ alkylene group.
 3. The secondary battery of claim 1, wherein m isan integer selected from 1 to
 100. 4. The secondary battery of claim 1,wherein a weight average molecular weight of the ionic liquid polymer isin a range of about 10,000 Daltons to about 100,000 Daltons.
 5. Thesecondary battery of claim 1, wherein the ionic liquid polymer isrepresented by Formula 2:

wherein, in Formula 2, R₁′, R₂′, and R₃′ are each independently selectedfrom a hydrogen atom, a halogen atom, a cyano group, a hydroxy group, asubstituted or unsubstituted C₁-C₂₀ alkyl group, a substituted orunsubstituted C₁-C₂₀ alkoxy group, a substituted or unsubstituted C₁-C₂₀heteroalkyl group, a substituted or unsubstituted C₃-C₂₀ cycloalkylgroup, a substituted or unsubstituted C₃-C₂₀ cycloalkyloxy group, asubstituted or unsubstituted C₃-C₃₀ heterocycloalkyl group, asubstituted or unsubstituted C₆-C₃₀ aryl group, an unsubstituted C₇-C₃₀arylalkyl group, a substituted or unsubstituted C₆-C₃₀ aryloxy group, asubstituted or unsubstituted C₃-C₃₀ heteroaryl group, a substituted orunsubstituted C₄-C₃₀ heteroarylalkyl group, a substituted orunsubstituted C₃-C₃₀ heteroaryloxy group, and a C₂-C₂₀ alkylene oxidegroup, and a combination thereof, provided that R′₃ is not an arylalkylgroup substituted with a C₂ alkene; p is an integer up to 500, q is aninteger selected from 1 to 100, wherein a weight average molecularweight of the ionic liquid polymer is in a range of about 10,000 Daltonsto about 1,000,000 Daltons; and X₁ ⁻ is at least one anion selected fromBF₄ ⁻, PF₆ ⁻, AsF₆ ⁻, SbF₆ ⁻, AlCl₄ ⁻, HSO₄ ⁻, CH₃SO₃ ⁻, (CF₃SO₂)₂N⁻,Cl⁻, Br⁻, I⁻, SO₄ ⁻, PF₆ ⁻, ClO₄ ⁻, CF₃SO₃ ⁻, CF₃CO₂ ⁻, (C₂F₅SO₂)₂N⁻,(C₂F₅SO₂)(CF₃SO₂)N⁻, (CF₃SO₂)₂N⁻, NO₃ ⁻, Al₂Cl₇ ⁻, AsF₆ ⁻, SbF₆ ⁻,CH₃COO⁻, (CF₃SO₂)₃C⁻, (CF₃)₂PF₄ ⁻, (CF₃)₃PF₃ ⁻, (CF₃)₄PF₂ ⁻, (CF₃)₅PF⁻,(CF₃)₆P⁻, SF₅CF₂SO₃ ⁻, SF₅CHFCF₂SO₃ ⁻, CF₃CF₂(CF₃)₂CO⁻, (CF₃SO₂)₂CH⁻,(SF₅)₃C⁻, and (O(CF₃)₂C₂(CF₃)₂O)₂PO⁻.
 6. The secondary battery of claim1, wherein the electrolyte comprises at least one selected from analkali metal salt and an alkaline earth metal salt.
 7. The secondarybattery of claim 6, wherein the at least one selected from an alkalimetal salt and an alkaline earth metal salt comprises at least oneselected from LiSCN, LiN(CN)₂, LiClO₄, LiBF₄, LiAsF₆, LiPF₆, LiCF₃SO₃,Li(CF₃SO₂)₂N, Li(CF₃SO₂)₃C, LiN(SO₂F)₂, LiN(SO₂CF₃)₂, LiN(SO₂CF₂CF₃)₂,LiSbF₆, LiPF₃(CF₂CF₃)₃, LiPF₃(CF₃)₃, LiB(C₂O₄)₂, NaSCN, NaSO₃CF₃, KTFSI,NaTFSI, Ba(TFSI)₂, Pb(TFSI)₂, and Ca(TFSI)₂.
 8. The secondary battery ofclaim 6, wherein an amount of the alkali metal salt and the alkalineearth metal salt is in a range of about 0.01 part by weight to about 100parts by weight based on 100 parts by weight of the ionic liquidpolymer.
 9. The secondary battery of claim 1, wherein the electrolytefurther comprises at least one selected from a liquid electrolyte, asolid electrolyte, a gel electrolyte, a plurality of inorganicparticles, and a separator.
 10. A method of preparing an electrolyte fora secondary battery, the method comprising: providing a monomerrepresented by Formula 3; in-situ polymerizing the monomer representedby Formula 3 to obtain the electrolyte according to claim 1;

wherein, in Formula 3, CY1 is selected from a substituted orunsubstituted non-fused 6-membered aromatic ring, a substituted orunsubstituted fused C₁₀-C₃₀ 6-membered aromatic ring, and a combinationof at least two of the foregoing aromatic rings, wherein the at leasttwo of the foregoing aromatic rings are linked through a single bond ora C₁-C₂₀ alkylene group; R₄ is selected from a halogen atom, a cyanogroup, a hydroxy group, a substituted or unsubstituted C₁-C₂₀ alkylgroup, a substituted or unsubstituted C₁-C₂₀ alkoxy group, a substitutedor unsubstituted heteroalkyl group, a substituted or unsubstitutedC₃-C₂₀ cycloalkyl group, a substituted or unsubstituted C₃-C₂₀cycloalkyloxy group, a substituted or unsubstituted C₃-C₃₀heterocycloalkyl group, a substituted or unsubstituted C₆-C₃₀ arylgroup, a substituted or unsubstituted C₇-C₃₀ arylalkyl group, asubstituted or unsubstituted C₆-C₃₀ aryloxy group, a substituted orunsubstituted C₃-C₃₀ heteroaryl group, a substituted or unsubstitutedC₄-C₃₀ heteroarylalkyl group, a substituted or unsubstituted C₃-C₃₀heteroaryloxy group, and a C₂-C₂₀ alkylene oxide group, and acombination thereof, provided that R₄ is not an arylalkyl groupsubstituted with a C₂ alkene; m₁ is an integer selected from 1 to 1,000;and X₂ ⁻ is at least one anion selected from BF₄ ⁻, PF₆ ⁻, AsF₆ ⁻, SbF₆⁻, AlCl₄ ⁻, HSO₄ ⁻, CH₃SO₃ ⁻, (CF₃SO₂)₂N⁻, Cl⁻, Br⁻, I⁻, SO₄ ⁻, PF₆ ⁻,ClO₄ ⁻, CF₃SO₃ ⁻, CF₃CO₂ ⁻, (C₂F₅SO₂)₂N⁻, (C₂F₅SO₂)(CF₃SO₂)N⁻,(CF₃SO₂)₂N⁻, NO₃ ⁻, Al₂Cl₇ ⁻, AsF₆ ⁻, SbF₆ ⁻, CH₃COO⁻, (CF₃SO₂)₃C⁻,(CF₃)₂PF₄ ⁻, (CF₃)₃PF₃ ⁻, (CF₃)₄PF₂ ⁻, (CF₃)₅PF⁻, (CF₃)₆P⁻, SF₅CF₂SO₃ ⁻,SF₅CHFCF₂SO₃ ⁻, CF₃CF₂(CF₃)₂CO⁻, (CF₃SO₂)₂CH⁻, (SF₅)₃C⁻, and(O(CF₃)₂C₂(CF₃)₂O)₂PO⁻.
 11. The method of claim 10, wherein the in-situpolymerizing comprises thermal in-situ polymerization or ultra-violetin-situ polymerization at room temperature.
 12. The method of claim 10,wherein the electrolyte further comprises at least one selected from analkali metal salt and an alkaline earth metal salt.
 13. The method ofclaim 12, wherein the at least one selected from an alkali metal saltand an alkaline earth metal salt comprises at least one selected fromLiSCN, LiN(CN)₂, LiClO₄, LiBF₄, LiAsF₆, LiPF₆, LiCF₃SO₃, Li(CF₃SO₂)₂N,Li(CF₃SO₂)₃C, LiN(SO₂F)₂, LiN(SO₂CF₃)₂, LiN(SO₂CF₂CF₃)₂, LiSbF₆,LiPF₃(CF₂CF₃)₃, LiPF₃(CF₃)₃, LiB(C₂O₄)₂, NaSCN, NaSO₃CF₃, KTFSI, NaTFSI,Ba(TFSI)₂, Pb(TFSI)₂, and Ca(TFSI)₂.
 14. The method of claim 12, whereinan amount of the alkali metal salt and the alkaline earth metal salt isin a range of about 0.01 part by weight to about 100 parts by weightbased on 100 parts by weight of the monomer for forming an ionic liquidpolymer.
 15. The secondary battery of claim 1, wherein the electrolytefurther comprises at least one selected from a liquid electrolyte, asolid electrolyte, a gel electrolyte, a plurality of inorganicparticles, and a separator.
 16. The secondary battery of claim 1,wherein a thickness of the layer, the film, or the sheet is in a rangeof about 0.1 micrometer to about 100 micrometers.
 17. The secondarybattery of claim 1, wherein an operation potential of the secondarybattery is in a range of about −0.1 Volts to about 4.5 Volts versusLi/Li⁺.